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• W26421855 abstract "Abstract Fe-ZSM-5 zeolites comprise of three types (I, II and III) of iron (Fe 3+ ) sites in both as synthesized (AS) and heat-treated states. Previous evidence could be confirmed by the assignment of ESR lines, registered in the X-band, stating: (i) type I framework Fe 3+ sites (in T h oxygen coordination), where charge compensation occurs mainly by Na + ions and the crystal field (cf) approximates cubic symmetry, produce resonances at near to g  = 2.00; (ii) type II and probably type III binuclear Fe...Fe dioxo- and oxo-bridges manifest themselves in producing slightly distorted surroundings of axial symmetry, and the relevant powder-averaged subspectrum is superimposed on the previous one in the g  ≅ 2.45–1.98 interval. As the temperature of the heat-treatment (HT) is raised, type II and III sites will be annihilated with preference, under concomitant production of amorphous Fe 2 O 3 possessing molecular dispersity. (iii) The weak ESR signal (2–4%) at g  ≅ 4.27 is attributed to T h coordinated framework sites in the surface layers (≈ 1 u.c. thick) under the influence of solid surface tension, giving rise to fully rhombic cf symmetry. The size of the ejected Fe 2 O 3 particles, as estimated from Mossbauer spectra (no hyperfine structure at 77 K) is less than 2.9 nm. The extremely large electron affinity of Fe 3+ ions manifests itself in decreased ionicity (and unexpectedly dominant cubic symmetry), activity in biomimetic oxidations, autoreduction and spontaneous reoxidation etc. In the liquid phase oxidation by hydrogen peroxide of n -hexane and cyclohexane the heat-treated Ti-ZSM-5 samples exhibited both activity- and selectivity dependence on HT. On the basis of experiences drawn from the heat-treatments proposal is made for the structures of the defect site (producing the 960 cm −1 IR signal) and the active centre of selective oxidation. The proposal seems to be in accord with the experimental observations (isotopic exchange, MAS-NMR behaviour etc.) published so far." @default.
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• W26421855 date "2000-01-01" @default.
• W26421855 modified "2023-10-16" @default.
• W26421855 title "Heat-treatment of isomorphously substituted ZSM-5 (MFI) zeolites" @default.
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• W26421855 doi "https://doi.org/10.1016/s0926-860x(99)00298-7" @default.
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